In-situ encapsulation and construction of Lac@HOFs/hydrogel composite for enhancing laccase stability and azo dyes decolorization efficiency

Enzymes with high catalytic activity and stability have been used for the sustainable development of green chemical applications, such as water remediation. Immobilized laccase can be used to construct a synergistic system for adsorption and degradation, which has great potential for water remediation. Herein, a hydrogen-bonded organic framework was installed onto laccase in-situ to form a net-carboxylate-arranged defective cage, which enhanced its catalytic stability. Thereafter, the CMC/PVA/Lac@HOF-101 hydrogel was fabricated by freeze-thaw cycles using sodium carboxymethylcellulose and polyvinyl alcohol as carriers and copper (II) as a cross-linker. Notably, the MOFs/hydrogel as a protective carrier of laccase maintain long-term recyclability and catalytic stability. After the fifth catalytic cycle, approximately 66.7 % activity of the CP-Lac@HOF-101 was retained. When both free laccase and CP-Lac@HOF-101 were used for decolorization of Acid Orange 7 (AO), the removal rates were 10.9 % and 82.5 % after 5 h, respectively. Furthermore, even in the presence of metal cations, almost 60.0 % of the AO removal efficiency was achieved. The relationship between the structure of the azo dyes and decolorization efficiency of the synergistic system was further investigated. This study offers a method for constructing enzyme@HOF-based composite hydrogels and provides a promising water remediation strategy.